US5795852A - Bar composition comprising nonionic polymeric surfacing as mildness enhancement agents - Google Patents

Bar composition comprising nonionic polymeric surfacing as mildness enhancement agents Download PDF

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US5795852A
US5795852A US08/637,145 US63714596A US5795852A US 5795852 A US5795852 A US 5795852A US 63714596 A US63714596 A US 63714596A US 5795852 A US5795852 A US 5795852A
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composition according
surfactant
anionic
bar
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Mengtao He
Michael Fair
Michael Massaro
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Lever Brothers Co
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Lever Brothers Co
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Assigned to LEVER BROTHERS COMPANY, DIVISION OF CONOPCO, INC. reassignment LEVER BROTHERS COMPANY, DIVISION OF CONOPCO, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FAIR, MICHAEL, HE, MENGTAO, MASSARO, MICHAEL
Priority to US08/637,145 priority Critical patent/US5795852A/en
Priority to DE69710064T priority patent/DE69710064T2/de
Priority to CA002248079A priority patent/CA2248079C/en
Priority to PCT/EP1997/001148 priority patent/WO1997040132A1/en
Priority to EP97908191A priority patent/EP0900269B1/en
Priority to AU20250/97A priority patent/AU728905B2/en
Priority to ES97908191T priority patent/ES2170367T3/es
Priority to BR9708736A priority patent/BR9708736A/pt
Priority to ARP970101612A priority patent/AR006776A1/es
Publication of US5795852A publication Critical patent/US5795852A/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/201—Monohydric alcohols linear
    • C11D3/2013—Monohydric alcohols linear fatty or with at least 8 carbon atoms in the alkyl chain
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/201—Monohydric alcohols linear
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/008—Polymeric surface-active agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/126—Acylisethionates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2044—Dihydric alcohols linear

Definitions

  • the present invention relates to synthetic bar compositions (i.e., bars in which at least some fatty acid soap has been replaced by synthetic surfactants, such as synthetic anionic surfactants).
  • soap has been utilized as a skin cleanser. Notwithstanding its many advantages (e.g., inexpensive, easy to manufacture into bars, having good lathering properties), soap is a very harsh chemical. Irritated and cracked skin often result from the use of soap, especially in colder climates.
  • anionic surfactants are still harsh.
  • One method of reducing the harshness of anionic surfactants is to utilize other surfactants such as nonionic or other mildness surfactants (e.g., amphoteric).
  • nonionic or other mildness surfactants e.g., amphoteric
  • amphoteric mildness surfactants
  • nonionic surfactants generally do not generate creamy thick lather as do anionics; and both nonionics and amphoterics, for example can be sticky and introduce processing difficulties.
  • the art is always searching for materials which are milder than anionic and/or which can be used to replace at least some of the anionic surfactants, yet, which do not simultaneously seriously compromise lather generation or processing efficiency. Further, even if the anionic is not substituted, the art is always searching for materials which can substitute for inerts and/or other fillers and produce enhanced mildness.
  • nonionic polymeric surfactants can be used to obtain these goals. That is, even at relatively low level of addition of nonionic polymeric surfactant (nonionic polymeric surfactant to anionic surfactant weight ratio below 1:1), the specified nonionic polymeric surfactants were found to significantly mitigate the skin irritation of anionic surfactants without sacrificing processability and lather. At weight ratios above 1:1, the bar processability can be negatively affected; for example, formulation can become highly viscous and sticky to cause extrusion difficulties.
  • hydrophobically modified nonionic polymers may be interacting with anionic surfactant to form polymer-surfactant complexes thereby reducing free anionic surfactant (known for its harshness) from the bar.
  • hydrophobically modified polyethylene glycol (HMPEG) nonionic polymeric surfactants in bar compositions per se is not new.
  • U.S. Pat. No. 3,312,627 to Hooker for example, teaches bars substantially free of anionic detergents comprising 0 to 70% by weight of polyethylene glycol (PEG) or hydrophobically modified derivatives of these compounds as base; and 10 to 70% of a nonionic lathering component.
  • PEG polyethylene glycol
  • the reference contemplates use of 10%-80% lithium soap. It is clear that use of lithium soap is unique to the invention (column 8, lines 20-23) and that use of other soaps or anionic (other than fatty acid lithium soap) is not contemplated. Thus, this reference clearly differs from the composition of the invention which comprise 10 to 70% of a surfactant system of which at least 50% (though no more than 60% total of total composition) is synthetic anionic surfactant.
  • World Patent No. WO 9317088 to Procter & Gamble claims a soap-based bar substantially free of synthetic anionic detergents comprising 45-90% fatty acid soap, 18% C 14-20 E 65-100 as coactive, and 0.5-2% cationic polymer as mildness aid.
  • the formulation had an improved scum control.
  • World Patent No. WO 9304161 to Procter & Gamble claims soap-based bar formulations substantially free of synthetic anionic detergents comprising 45-90% fatty acid soap, 0.5-10% C 14-20 E 20-250 (preferably C 14-20 E 25-80 ) as coactive, and 0.5-10% acyl isethionate surfactant.
  • the addition of small amounts of ethoxylated nonionic surfactant was to reduce the scum formation.
  • European Patent No. EP 311,343 to G. Dawson and G. Ridley teaches a Betaphase toilet soap bar substantially free of synthetic anionic detergents comprising 45-90% of soluble alkali metal soap of C8-C24 fatty acids, 0.5-45% of an ethoxylated nonionic surfactant having an HLB of 12-19.5, and 0.01 to 5% of a water-soluble polymer.
  • the composition has improved scum control with good mildness, lathering, and transparency.
  • hydrophobically modified polyalkylene glycols weight ratio well below 1:1
  • the alkylene oxide adduct of our choice can still significantly reduce the skin irritation potential of anionic surfactant.
  • This low addition level is a criticality, because at higher level of addition, defined hydrophobically modified polyalkylene glycols can make bar formulation sticky and viscous thereby causing processing problems, such as difficulties during extrusion and stamping.
  • HMPEG hydrophobically modified polyethylene glycol
  • a surfactant system selected from the group consisting of anionic surfactants, nonionic surfactants (other than the hydrophobically modified polyethylene glycols), cationic surfactants, amphoteric surfactants and mixtures thereof;
  • anionic surfactant comprises at least 50%, preferably at least 60% of said surfactant system and wherein the anionic component further comprises no more than about 60% by wt. of total composition;
  • bar structurant selected from the group consisting of alkylene oxide compounds having a molecular weight of from about 2000 to about 25,000, preferably 3,000 to 10,000; C 8 -C 22 free fatty acids, paraffin waxes; water soluble starches (e.g., maltodextrin); and C 8 -C 20 alkanols; and
  • the weight ratio of HMPEG to anionic surfactant is between 1:1.5 to 1:10, preferably 1:3 to 1:7. Above the range of this weight ratio, bar processability can be negatively affected, e.g., increased stickiness causes plodding and stamping difficulties; below the range of this ratio, the skin irritation of anionic surfactants can not be effectively mitigated.
  • composition may optionally comprise 0% to 25%, preferably 2% to 15% by wt. solvent such as ethylene oxide or propylene oxide.
  • FIG. 1a and FIG. 1b shows the Zein % dissolved by acyl isethionate/cocoamidopropyl betaine as a function of nonionic polymeric surfactant concentration.
  • POE(200) glyceryl stearate and POE(200) glyceryl tallowate significantly reduced the Zein % dissolved at relatively low levels. Therefore the irritation potential of a personal washing bar can be further reduced by including relatively low levels (i.e., HMPEG: anionic weight ratio below 1:1) of defined hydrophobically modified polyalkylene glycols in a full bar composition.
  • FIG. 2 shows the HMPEG of the invention significantly reduces skin irritation caused by sodium acyl isethionate at low levels of addition (i.e., HMPEG: anionic weight ratio below 1:1).
  • the present invention relates to synthetic bar compositions wherein the majority of the surfactant system of the bar comprises synthetic anionic surfactant; and to specific hydrophobically modified polyalkylene glycols which can be used in such bar compositions at relatively low addition levels to significantly enhance bar mildness without sacrificing processability and lather.
  • the bar compositions comprise
  • a surfactant system wherein said surfactant system is selected from the group consisting of anionic surfactants, nonionic surfactants (other than the EO-PO polymer), amphoteric surfactants, cationic surfactants and mixtures thereof, wherein the anionic comprises 50% or more, preferably 60% or more, of the surfactant system and the anionic further comprises no more than 60% of the total composition;
  • a bar structurant selected from the group consisting of polyalkylene glycols having a MW of from about 2,000 to 25,000 (which may optionally include 1% to 5% higher molecular weight polyalkylene glycols having MW from 50,000 to 500,000, especially around 100,000); C 8 to C 24 , preferably C 12 to C 24 fatty acids; paraffin waxes; water soluble starches (e.g., maltodextrin); and C 8 to C 20 alkanols (e.g., cetyl alcohol); and
  • weight ratio of hydrophobically modified polyalkylene glycol to anionic surfactant is between 1:1.5 to 1:10, preferably 1:3 to 1:7. Above the range of this weight ratio, bar processability can be negatively affected, e.g., increased stickiness may cause plodding and stamping difficulties; below the range of this ratio, the skin irritation of anionic surfactants can not be effectively mitigated.
  • the anionic detergent active which may be used may be aliphatic sulfonates, such as a primary alkane (e.g., C 8 -C 22 ) sulfonate, primary alkane (e.g., C 8 -C 22 ) disulfonate, C 8 -C 22 alkene sulfonate, C 8 -C 22 hydroxyalkane sulfonate or alkyl glycerol ether sulfonate (AGS); or aromatic sulfonates such as alkyl benzene sulfonate.
  • a primary alkane e.g., C 8 -C 22
  • primary alkane e.g., C 8 -C 22
  • disulfonate C 8 -C 22 alkene sulfonate
  • C 8 -C 22 hydroxyalkane sulfonate C 8 -C 22 hydroxyalkane sulfonate
  • the anionic may also be an alkyl sulfate (e.g., C 12 -C 18 alkyl sulfate) or alkyl ether sulfate (including alkyl glycerol ether sulfates). among the alkyl ether sulfates are those having the formula:
  • R is an alkyl or alkenyl having 8 to 18 carbons, preferably 12 to 18 carbons, n has an average value of greater than 1.0, preferably greater than 3; and M is a solubilizing cation such as sodium, potassium ammonium or substituted ammonium. Ammonium and sodium lauryl ether sulfates are preferred.
  • the anionic may also be alkyl sulfosuccinates (including mono- and dialkyl, e.g., C 6 -C 22 sulfosuccinates); alkyl and acyl taurates, alkyl and acyl sarcosinates, sulfoacetates, C 8 -C 22 alkyl phosphates and phosphates, alkyl phosphate esters and alkoxyl alkyl phosphate esters, acyl lactates, C 8 -C 22 monoalkyl succinates and maleates, sulphoacetates, alkyl glucosides and acyl isethionates.
  • alkyl sulfosuccinates including mono- and dialkyl, e.g., C 6 -C 22 sulfosuccinates
  • alkyl and acyl taurates alkyl and acyl sarcosinates
  • Sulfosuccinates may be monoalkyl sulfosuccinates having the formula:
  • R 4 ranges from C 8 -C 22 alkyl and M is a solubilizing cation.
  • R ranges from C 8 -C 20 alkyl and M is a solubilizing cation.
  • Taurates are generally identified by formula:
  • R 2 ranges from C 8 -C 18 alkyl
  • R 3 ranges from C 1 -C 4 a alkyl
  • M is a solubilizing cation.
  • esters are prepared by reaction between alkali metal isethionate with mixed aliphatic fatty acids having from 6 to 18 carbon atoms and an iodine value of less than 20. At least 75% of the mixed fatty acids have from 12 to 18 carbon atoms and up to 25% have from 6 to 10 carbon atoms.
  • Acyl isethionates when present, will generally range from about 10% to about 70% by weight of the total composition. Preferably, this component is present from about 30% to about 60%.
  • the acyl isethionate may be an alkoxylated isethionate such as is described in liardi et al., U.S. Pat. No. 5,393,466, hereby incorporated by reference.
  • This compound has the general formula: ##STR1## wherein R is an alkyl group having 8 to 18 carbons, m is an integer from 1 to 4, X and Y are hydrogen or an alkyl group having 1 to 4 carbons and M + is a monovalent cation such as, for example, sodium, potassium or ammonium.
  • the anionic surfactant comprises 50% or more of the total surfactant system, but should comprise no more than 40% by wt. of the total composition.
  • Amphoteric detergents which may be used in this invention include at least one acid group. This may be a carboxylic or a sulphonic acid group. They include quaternary nitrogen and therefore are quaternary amido acids. They should generally include an alkyl or alkenyl group of 7 to 18 carbon atoms. They will usually comply with an overall structural formula. ##STR2## where R 1 is alkyl or alkenyl of 7 to 18 carbon atoms;
  • R 2 and R 3 are each independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 3 carbon atoms;
  • n 2 to 4.
  • n 0 to 1;
  • X is alkylene of 1 to 3 carbon atoms optionally substituted with hydroxyl
  • Y is --CO 2 -- or --SO 3 --
  • Suitable amphoteric detergents within the above general formula include simple betaines of formula: ##STR3## and amido betaines of formula: ##STR4## wherein m is 2 or 3.
  • R 1 may in particular be a mixture of C 12 and C 14 alkyl groups derived from coconut so that at least half, preferably at least three quarters of the groups R 1 are preferably methyl.
  • amphoteric detergent is a sulphobetaine of formula ##STR5## wherein m is 2 or 3, or variants of these in which --(CH 2 ) 3 SO 3 is replaced by ##STR6##
  • R 1 , R 2 and R 3 are as discussed previously.
  • the nonionic which may be used includes in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • nonionic detergent compounds are alkyl (C 6 -C 22 ) phenols-ethylene oxide condensates, the condensation products of aliphatic (C 8 C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamene
  • nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
  • the nonionic may also be a sugar amide, such as a polysaccharide amide.
  • the surfactant may be one of the lactobionamides described in U.S. Pat. No. 5,389,279 to Au et al. which is hereby incorporated by reference or it may be one of the sugar amides described in U.S Pat. No. 5,009,814 to Kelkenberg, hereby incorporated into the subject application by reference.
  • Nonionic and cationic surfactants which may be used include any one of those described in U.S. Pat. No. 3,761,418 to Parran, Jr. hereby incorporated by reference into the subject application. Those included are the aldobionamides taught in U.S. Pat. No. 5,389,279 to Au et al. and the polyhydroxy fatty acid amides as taught in U.S. Pat. No. 5,312,934 to Lefton, both of which are incorporated by reference into the subject application.
  • the surfactants generally comprise 10 to 50% of the total composition except, as noted that anionic comprises 50% or more of the surfactant system and no more than 40% total.
  • a preferred surfactant system is one comprising acyl isethionate and a amphoteric, i.e., betaine, as co-surfactant.
  • the structurant of the invention can be a water soluble or water insoluble structurant.
  • Water soluble structurants include moderately high molecular weight polyalkylene oxides of appropriate melting point (e.g., 40° to 100° C., preferably 50° to 90°) and in particular polyethylene glycols or mixtures thereof.
  • Polyethylene glycols which are used may have a molecular weight in the range 2,000 to 25,000, preferably 3,000 to 10,000. However, in some embodiments of this invention it is preferred to include a fairly small quantity of polyethylene glycol with a molecular weight in the range from 50,000 to 500,000, especially molecular weights of around 100,000. Such polyethylene glycols have been found to improve the wear rate of the bars. It is believed that this is because their long polymer chains remain entangled even when the bar composition is wetted during use.
  • the quantity is preferably from 1% to 5%, more preferably from 1% or 1.5% to 4% or 4.5% by weight of the composition.
  • these materials will generally be used jointly with a large quantity of other water soluble structurant such as the above mentioned polyethylene glycol of molecular weight 2,000 to 25,000, preferably 3,000 to 10,000.
  • Water insoluble structurants also have a melting point in the range 40°-100° C., more preferably at least 50° C., notably 50° C. to 90° C.
  • Suitable materials which are particularly envisaged are fatty acids, particularly those having a carbon chain of 12 to 24 carbon atoms. Examples are lauric, myristic, palmitic, stearic, arachidic and behenic acids and mixtures thereof. Sources of these fatty acids are coconut, topped coconut, palm, palm kernel, babassu and tallow fatty acids and partially or fully hardened fatty acids or distilled fatty acids.
  • Other suitable water insoluble structurants include alkanols of 8 to 20 carbon atoms, particularly cetyl alcohol. These materials generally have a water solubility of less than 5 g/liter at 20° C.
  • Soaps e.g., sodium stearate
  • the soaps may be added neat or made in situ by adding a base, e.g., NaOH, to convert free fatty acids.
  • the relative proportions of the water soluble structurants and water insoluble structurants govern the rate at which the bar wears during use.
  • the presence of the water-insoluble structurant tends to delay dissolution of the bar when exposed to water during use and hence retard the rate of wear.
  • the structurant is used in the bar in an amount of 20% to 85%, preferably 30% to 70% by wt.
  • the hydrophobically modified polyalkylene glycols (HMPEG) of the subject invention are generally commercially available nonionic polymeric surfactants having a broad molecular weight range from about 3000 to 25000 (preferably 4000 to 15000) and a melting temperature of from about 25° to 85° C., preferably 40° to 65° C. Below the defined range of molecular weight, HMPEG can make bar formulations sticky and therefore cause processing problems, such as difficulties in extrusion and stamping. Above this range, HMPEG can make bar formulation highly viscous and may cause mixing difficulties.
  • the polymers will be selected from alkylene nonionic polymers chemically terminally attached by hydrophobic moieties.
  • hydrophobic moieties R
  • These polymers are usually commercially available.
  • the portion of ethylene oxide moiety per mole is between 60% wt. and 99% wt. (preferably 85% wt. to 97% wt.).
  • the total content of the hydrophobic moiety is between 2% wt. and 30% wt. (preferably 3% wt. to 15% wt.) in each mole of hydrophobically modified alkylene glycol.
  • the hydrophobic moiety (or moieties) may be derivatives of linear or branched alkyls, acyls, and aryl, alkylaryl, and alkenyls having 2 to 60 carbons, preferably 8 to 40 carbons. Detailed description of the hydrophobic moiety (moieties) is presented in Table 1.
  • examples of various hydrophobically modified polyalkylene glycols are set forth in Table 1 below wherein T m (°C.) were digested from literature from the corresponding chemical suppliers or measured by the inventors using a differential scanning calorimetry technique.
  • R hydrophobic moieties, such as derivatives of alkyl, aryl, alkylaryl, alkylene, acyl; and fat and oil derivatives of alkylglyceryl, glyceryl, sorbitol, lanolin oil, coconut oil, jojoba oil, castor oil, almond oil, peanut oil, wheat germ oil, rice bran oil, linseed oil, apricot pits oil, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil, soybean oil, avocado oil, sunflower seed oil, hazelnut oil, olive oil, grapeseed oil, and safflower oil, Shea butter, babassu oil, etc.;
  • POE Polyoxyethylene or polyethylene glycol
  • melting temperature of the compounds must be about 25° C.-85° C., preferably 40° C. to 65° C., the latter being more favorable for processing (e.g., chips form more easily and logs plod more readily).
  • Bars of the invention may comprise 0% to 25%, preferably 2% to 15% by wt. of an emollient such as ethylene glycol, propylene glycol and/or glycerine.
  • an emollient such as ethylene glycol, propylene glycol and/or glycerine.
  • Bar compositions of this invention will usually contain water, but the amount of water is only a fairly small proportion of the bar. Larger quantities of water reduce the hardness of the bars. Preferred is that the quantity of water is not over 15% by weight of the bars, preferably 1% to about 10%, more preferably 3% to 9%, most preferably 3% to 8%.
  • Bars of this invention may optionally include so-called benefit agents--materials included in relatively small proportions which confer some benefit additional to the basic cleansing action of the bars.
  • benefit agents include so-called skin conditioning agents, including emollients such as fatty alcohols and vegetable oils, essential oils, waxes, phospholipids, lanolin, anti-bacterial agents and sanitizers, opacifiers, pearlescers, electrolytes, perfumes, sunscreens, fluorescers and coloring agents.
  • skin conditioning agents comprise silicone oils, mineral oils and/or glycerol.
  • Zein dissolution test was used to preliminarily screen the irritation potential of the formulations studied.
  • 30 mLs of an aqueous dispersion of a formulation were prepared.
  • the dispersions sat in a 45° C. bath until fully dissolved.
  • 1.5 gms of zein powder were added to each solution with rapid stirring for one hour.
  • the solutions were then transferred to centrifuge tubes and centrifuged for 30 minutes at approximately 3,000 rpms.
  • the undissolved zein was isolated, rinsed and allowed to dry in a 60° C. vacuum oven to a constant weight.
  • the percent zein solubilized which is proportional to irritation potential, was determined gravimetrically.
  • Patch test was used to evaluate skin mildness of aqueous dispersions containing 1% DEFI active (sodium cocoyl isethionate) and different levels of the structurant/coactives.
  • Patches Hilltop® Chambers, 25 mm in size
  • the patches were removed and the sites were visually ranked in order of severity (erythema and dryness) by trained examiners under consistent lighting.
  • Bar formulations were prepared in a 2-liter Patterson mixer with a sigma type blade. The components were mixed together at -95° C., and the water level was adjusted to approximately 8-10 wt. %. The batch was covered to prevent moisture loss, and mixed for about 15 minutes. Then the cover was removed and the mixture was allowed to dry. The moisture content of the samples taken at different times during the drying stage was determined by Karl Fisher titration with a turbo titrator. At the final moisture level (-5%), the formulation was dropped onto a heated applicator roll and then was chipped over a chill roll. The chill roll chips were plodded under vacuum in a Weber Seelander duplex refiner with screw speed at -20 rpm. The nose cone of the plodder was heated to 45°-50° C. The cut billets were stamped into bars using a Weber Seelander L4 hydraulic press with a nylon, pillow-shaped die in place.
  • Bars were also prepared by a cast-melt process.
  • the components were mixed together at 80°-120° C. in a 500 ml beaker, and the water level was adjusted to approximately 10-15 wt. %.
  • the batch was covered to prevent moisture loss and was mixed for about 15 minutes. Then the cover was removed, and the mixture was allowed to dry.
  • the moisture content of the samples taken at different times during the drying stage and was determined by Karl Fisher titration with a turbo titrator.
  • the mixture in the beaker in the form of a free-flow liquid
  • hydrophobically modified polyalkylene glycols were investigated using Zein dissolution experiments. As indicated in FIG. 1a and FIG. 1b, the defined hydrophobically modified polyalkylene glycols, as a class, are significantly more effective than PEG in reducing the Zein % dissolved by 1% to 2% aqueous DEFI suspension (DEFI is a sodium acyl isethionate/fatty acid mixture defined in the Table 2 of Example 1). The data in FIG. 1a and FIG.
  • hydrophobically modified polyalkylene glycols significantly reduced the amount of Zein dissolved by DEFI.
  • HMPEG namely POE(200) glyceryl stearate
  • POE(200) glyceryl stearate significantly reduced the skin irritation caused by sodium acyl isethionate, even at low levels of addition.
  • SAI sodium acyl isethionate
  • POE(200) glyceryl stearate reduced the skin irritation of a DEFI/betaine liquor significantly.

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  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Detergent Compositions (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
US08/637,145 1996-04-24 1996-04-24 Bar composition comprising nonionic polymeric surfacing as mildness enhancement agents Expired - Fee Related US5795852A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US08/637,145 US5795852A (en) 1996-04-24 1996-04-24 Bar composition comprising nonionic polymeric surfacing as mildness enhancement agents
EP97908191A EP0900269B1 (en) 1996-04-24 1997-03-06 Bar composition comprising nonionic polymeric surfactants as mildness enhancement agents
CA002248079A CA2248079C (en) 1996-04-24 1997-03-06 Bar composition comprising nonionic polymeric surfactants as mildness enhancement agents
PCT/EP1997/001148 WO1997040132A1 (en) 1996-04-24 1997-03-06 Bar composition comprising nonionic polymeric surfactants as mildness enhancement agents
DE69710064T DE69710064T2 (de) 1996-04-24 1997-03-06 Stückförmige zusammensetzung enthaltend nichtionische polymertenside als sanftmittel
AU20250/97A AU728905B2 (en) 1996-04-24 1997-03-06 Bar composition comprising nonionic polymeric surfactants as mildness enhancement agents
ES97908191T ES2170367T3 (es) 1996-04-24 1997-03-06 Composiciones en forma de pastilla que comprenden agentes tensioactivos polimericos no ionicos como agentes potenciadores de la suavidad.
BR9708736A BR9708736A (pt) 1996-04-24 1997-03-06 Composição em barra
ARP970101612A AR006776A1 (es) 1996-04-24 1997-04-22 Una composicion en barra

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US5935917A (en) * 1996-06-26 1999-08-10 Lever Brothers Company Bar composition comprising entrapped emollient droplets dispersed therein
US5972859A (en) * 1996-06-26 1999-10-26 Lever Brothers Company Bar composition comprising entrapped emollient droplets dispersed therein
US6121216A (en) * 1996-07-11 2000-09-19 Lever Brothers Company, Division Of Conopco, Inc. Enhanced processing of synthetic bar compositions comprising amphoterics based on minimal levels of fatty acid soap and minimum ratios of saturated to unsaturated soap
US6214780B1 (en) 2000-03-08 2001-04-10 Lever Brothers Company, Division Of Conopco, Inc. Enhanced processing of synthetic bar compositions comprising amphoterics based on minimal levels of fatty acid soap and minimum ratios of saturated to unsaturated soap
US6248703B1 (en) * 2000-03-15 2001-06-19 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Extruded soap and/or detergent bar compositions comprising encapsulated benefit agent
US6469371B2 (en) 2000-01-05 2002-10-22 Shinko Electric Industries Co., Ltd. Non-contact type IC card and process for manufacturing same
US6475979B2 (en) 1999-10-20 2002-11-05 Grain Processing Corporation Reduced malto-oligosaccharide cleansing compositions
US6610672B2 (en) 1999-10-20 2003-08-26 Grain Processing Corporation Compositions including reduced malto-oligosaccharide preserving agents, and methods for preserving a material
US6613898B1 (en) 1998-01-20 2003-09-02 Grain Processing Corporation Reduced malto-oligosaccharides
US6706675B1 (en) 2002-08-30 2004-03-16 The Dial Corporation Translucent soap bar composition and method of making the same
US6720418B2 (en) 1999-08-20 2004-04-13 Grain Processing Corporation Derivatized reduced malto-oligosaccharides
US6919446B1 (en) 1998-01-20 2005-07-19 Grain Processing Corp. Reduced malto-oligosaccharides
US20080095807A1 (en) * 2006-01-03 2008-04-24 Erez Zabari Cosmetic soap
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US6362145B1 (en) * 2000-11-14 2002-03-26 Clariant International Ltd. Clear soap bar comprising metal catalyst sodium cocoyl isethionate

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5935917A (en) * 1996-06-26 1999-08-10 Lever Brothers Company Bar composition comprising entrapped emollient droplets dispersed therein
US5972859A (en) * 1996-06-26 1999-10-26 Lever Brothers Company Bar composition comprising entrapped emollient droplets dispersed therein
US6121216A (en) * 1996-07-11 2000-09-19 Lever Brothers Company, Division Of Conopco, Inc. Enhanced processing of synthetic bar compositions comprising amphoterics based on minimal levels of fatty acid soap and minimum ratios of saturated to unsaturated soap
US6919446B1 (en) 1998-01-20 2005-07-19 Grain Processing Corp. Reduced malto-oligosaccharides
US7595393B2 (en) 1998-01-20 2009-09-29 Grain Processing Corporation Reduced malto-oligosaccharides
US7405293B1 (en) 1998-01-20 2008-07-29 Grain Processing Corporation Reduced malto-oligosaccharides
US20050143573A1 (en) * 1998-01-20 2005-06-30 Grain Processing Corporation Reduced malto-oligosaccharides
US6613898B1 (en) 1998-01-20 2003-09-02 Grain Processing Corporation Reduced malto-oligosaccharides
US6720418B2 (en) 1999-08-20 2004-04-13 Grain Processing Corporation Derivatized reduced malto-oligosaccharides
US6610672B2 (en) 1999-10-20 2003-08-26 Grain Processing Corporation Compositions including reduced malto-oligosaccharide preserving agents, and methods for preserving a material
US6475979B2 (en) 1999-10-20 2002-11-05 Grain Processing Corporation Reduced malto-oligosaccharide cleansing compositions
US6469371B2 (en) 2000-01-05 2002-10-22 Shinko Electric Industries Co., Ltd. Non-contact type IC card and process for manufacturing same
US6214780B1 (en) 2000-03-08 2001-04-10 Lever Brothers Company, Division Of Conopco, Inc. Enhanced processing of synthetic bar compositions comprising amphoterics based on minimal levels of fatty acid soap and minimum ratios of saturated to unsaturated soap
US6248703B1 (en) * 2000-03-15 2001-06-19 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Extruded soap and/or detergent bar compositions comprising encapsulated benefit agent
US6706675B1 (en) 2002-08-30 2004-03-16 The Dial Corporation Translucent soap bar composition and method of making the same
US20080095807A1 (en) * 2006-01-03 2008-04-24 Erez Zabari Cosmetic soap
WO2018104115A1 (en) 2016-12-06 2018-06-14 Unilever Plc Synthetic detergent bars
US11384320B2 (en) 2016-12-06 2022-07-12 Conopco, Inc. Synthetic detergent bars

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AU2025097A (en) 1997-11-12
ES2170367T3 (es) 2002-08-01
CA2248079A1 (en) 1997-10-30
DE69710064D1 (de) 2002-03-14
AR006776A1 (es) 1999-09-29
CA2248079C (en) 2006-10-17
EP0900269B1 (en) 2002-01-23
WO1997040132A1 (en) 1997-10-30
AU728905B2 (en) 2001-01-18
EP0900269A1 (en) 1999-03-10
BR9708736A (pt) 1999-08-03
DE69710064T2 (de) 2002-06-20

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